In U.S. Pat. No. 4,709,054, there is described a method for silylating aromatic acylhalide with halogenated polysilane in the presence of an effective amount of a transition metal catalyst. As shown by Yamamoto et al., Tetrahedron Letters, 1653 (1980) activated aromatic acylhalide, such as para-nitrobenzoylchloride, can be converted to the corresponding aromatic silane with a loss of carbon monoxide as a result of a decarbonylation reaction utilizing hexamethyldisilane as the silylating reactant. It was found, however, that the silylation of the aromatic nucleus using hexamethyl disilane, resulted in only a minor amount of the desired aromatic silane, such as a paranitrophenyltrimethylsilane, while the major product was the corresponding aromatic silylketone.
In U.S. Pat. No. 4,709,054 (Rich), assigned to the same assignee as the present invention and incorporated herein by reference, there is taught that if halogenated polysilane of the formula, ##STR1## is reacted with aromatic acylhalide of the formula, ##STR2## in the presence of an effective amount of a transition metal catalyst, a wide variety of aromatic silylation reaction products can be obtained at high yields resulting in the production of nuclear-bound carbon-silicon bonds, where X is a halogen radical, R is selected from X, hydrogen, C.sub.(1-13) monovalent hydrocarbon radicals, substituted C.sub.(1-13) monovalent hydrocarbon radicals, and divalent --O--, --S-- radicals and mixtures thereof which can form .tbd.SiOSi.tbd. and .tbd.SiSSi.tbd. connecting groups, R.sup.1 is a C.sub.(6-20) monovalent or polyvalent aromatic organic radical, n is an integer equal to 1 to 50 inclusive, and m is an integer equal to 1 to 4 inclusive.
Although the method of U.S. Pat. No. 4,709,054 provides for the production of organic salines and silarylenes at high yields, it has been found difficult to recycle, regenerate or salvage transition metal catalyst values from the reaction mixture.
In copending application, Ser. No. 033,567, there is discussed the use of a transition metal complex supported by an inorganic substrate having chemically combined groups of the formula, ##STR3## where R.sup.2 is a divalent C.sub.(2-14) organic radical, Q is a nitrogen or phosphorous radical, R.sup.3 and R.sup.4 are monovalent C.sub.(1-14) alkyl or aryl radicals, M is a transition metal selected from palladium, platinum, rhodium or nickel, X is previously defined, y is an integer equal to 1 to 3 inclusive and preferably 2.
The present invention is based on the discovery that a wide variety of silylated aromatic reaction products having one or more nuclear-bound silicon atoms joined to an aromatic nucleus by carbon-silicon bonds also can be made by effecting reaction between halogenated polysilane of formula (1) and aromatic acylhalide of formula (2) in the presence of an effective amount of a transition metal complex supported by an organic substrate. Support to an organic substrate can be achieved through chemically combined groups of the formula ##STR4## where R.sup.2, R.sup.3, and R.sup.4, M, X and y are as previously defined. Surprisingly, supported transition metal complexes of the present invention having chemically combined groups of formulas (3) or (4) have been found to be recyclable at the termination of the reaction. In addition, supported complexes having chemically combined groups of formula (3) also can be regenerated at the end of the reaction.